WO1998044014A1 - Polyurethanes et polyesters de polyols - Google Patents

Polyurethanes et polyesters de polyols Download PDF

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Publication number
WO1998044014A1
WO1998044014A1 PCT/JP1998/001061 JP9801061W WO9844014A1 WO 1998044014 A1 WO1998044014 A1 WO 1998044014A1 JP 9801061 W JP9801061 W JP 9801061W WO 9844014 A1 WO9844014 A1 WO 9844014A1
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WO
WIPO (PCT)
Prior art keywords
acid
polyester polyol
formula
polyurethane
dialkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1998/001061
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English (en)
Japanese (ja)
Inventor
Shigeru Murata
Yukio Inaba
Masahiko Yasuda
Tetsuya Nakajima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KH Neochem Co Ltd
Original Assignee
Kyowa Yuka Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyowa Yuka Co Ltd filed Critical Kyowa Yuka Co Ltd
Priority to EP98907214A priority Critical patent/EP0908481A4/fr
Priority to CA002256627A priority patent/CA2256627C/fr
Priority to US09/194,394 priority patent/US6087466A/en
Priority to KR1019980709243A priority patent/KR100306048B1/ko
Priority to AU63110/98A priority patent/AU710285B2/en
Priority to JP54140398A priority patent/JP3920930B2/ja
Publication of WO1998044014A1 publication Critical patent/WO1998044014A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to extrusion molding materials such as hoses, tubes, films, sheets, belts, and rolls, packing materials, injection molding materials for machine parts, automobile parts, etc., and coating materials such as artificial leather, paints, and adhesives.
  • the present invention relates to a polyurethane and a polyester polyol excellent in hydrolysis resistance, alkali resistance and mechanical strength, which are useful as a material. Background art
  • Polyurethane is produced by reacting a polyester polyol, polyether polyol and polyisocyanate in the presence of a chain extender such as a low molecular weight diol or diamine if necessary.
  • a chain extender such as a low molecular weight diol or diamine if necessary.
  • Polyurethanes using polyester polyols have poorer hydrolysis resistance than polyurethanes using polyether polyols, while polyurethanes using polyether polyols have mechanical properties, weather resistance, oil resistance, and oil resistance. There is a problem with solvent properties, and its use is limited.
  • Polyurethanes using polycarbonate polyols improve the above-mentioned disadvantages, but have insufficient cold resistance and are extremely expensive, so that their industrial use is limited.
  • polyester-based polyurethane derived from a chain diol having an alkyl side chain examples include, for example, neopentyl glycol or polyester-based polyurethane derived from 2-butyl-2-ethyl-1,3-propanediol (Japanese Unexamined Patent Publication No. — Patent No. 2 229 918) and 3-methyl-1,5-pentanediol-derived polyester-based polyurethanes (Japanese Patent Publication No. 3_5 496 6) are known, but they are not practical. However, it is not satisfactory in terms of water resistance and the like.
  • JP-A-4-18141 and JP-A-5-262859 disclose polyester-based polyolefins derived from a chain diol having an alkyl side chain.
  • 2,4-dialkyl-1,5- There is no specific disclosure of polyurethane made from a polyester copolymer derived from pentanediol and 2,2-dialkyl-1,3-propanediol.
  • WO96Z09334 discloses a polyester polyurethane derived from 2,4-getyl-1,5-pentanediol as a polyurethane having excellent hydrolysis resistance, weather resistance and alkali resistance.
  • Polyurethanes described in the examples of this publication using 2,4-diethyl-1,5-pentanediol alone as a diol component as a raw material for polyester polyols exhibit practically satisfactory performance in many applications. However, when used in applications such as undersea cable for oil exploration used under severe conditions, connection cords for electric heavy machinery, etc. Is not satisfactory.
  • the polyurethane of the present invention is a polyurethane having in its molecule a polyester moiety having both a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II).
  • R 1 and R 2 are the same or different and represent lower alkyl having 1 to 8 carbon atoms.
  • R 3 and R 4 are the same or different and represent lower alkyl having 1 to 8 carbon atoms).
  • the polyurethane Since the polyurethane has both structural units represented by the formula (I) and the formula (II) in the molecule of the polyurethane, the polyurethane is excellent in breaking strength, hydrolysis resistance, and the like. Further, according to the present invention, there is provided a polyester polyol for producing the polyurethane, the polyester polyol having both structural units represented by the formulas (I) and (II) in a molecule.
  • the polyester polyol is produced by dehydration polycondensation of a mixed diol obtained by mixing 2,4-dialkyl-1,5-pentanediol and 2,2-dialkyl-1,1-propanediol with a dicarboxylic acid component. it can. BEST MODE FOR CARRYING OUT THE INVENTION
  • the lower alkyl having 1 to 8 carbon atoms represents a straight-chain or branched one, for example, methyl, ethyl, propyl, isopropyl, butyl, Examples include isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, neopentyl, 2-pentyl, 3-pentyl, hexyl, heptyl, and octyl.
  • the polyester polyol of the present invention comprises 2,4-dialkyl-1,5-pentanedole, which is a component capable of providing the structural unit represented by the general formula (I), and a compound represented by the general formula (II).
  • a mixed diol of 2,2-dialkyl-1,3-propanediol, which is a component capable of providing a structural unit to be obtained, and dicarbonic acid are prepared by a known method, for example, as described in JP-A-48-101496. Can be produced by subjecting it to an esterification reaction according to the method described in the above.
  • the structural unit represented by the general formula (I) may be an esterification reaction of 2,4-dialkyl-1,5-benzenediol with a dicarboxylic acid or a dicarboxylic acid ester. Is formed by a transesterification reaction or the like. On the other hand, the structural unit represented by the general formula (II) is formed by an esterification reaction or a transesterification reaction of 2,2-dialkyl-1,3-propanediol with a dicarboxylic acid or a dicarboxylic acid ester. You.
  • the polyester polyol of the present invention has both a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) in a molecule.
  • the polyester polyol of the present invention can be obtained, for example, by first performing a partial esterification reaction, and further subjecting the resulting reaction product to an esterification reaction at a higher temperature and under reduced pressure. At that time, a known esterification catalyst may be allowed to coexist.
  • the esterification reaction is preferably carried out at 150-250, more preferably at 180-230 ° C.
  • either one of 2,4-dialkyl-1,5-pentanediol and 2,2-dialkyl-1,3-propanediol is subjected to an esterification reaction with a dicarboxylic acid first, followed by a reaction with the remaining one.
  • the polyester polyol of the present invention can be obtained also by adding one of the diols and reacting with the dicarboxylic acid.
  • the polyester polyol of the present invention may be a mixture of 2,4-dialkyl-1,5-pentanediol and 2,2-dialkyl-1,3-propanediol with a methyl ester of dicarboxylic acid, methyl ester, ethyl ester, or the like.
  • the polyester polyol of the present invention comprises a 2,4-dialkyl-1,5-pentanediol, a 2,2-dialkyl-1,3-propanediol, and a random mixture of a dicarboxylic acid with another diol optionally added. It is a copolymer or a block copolymer.
  • 2,4-dialkyl-1,5-pentanediol examples include 2,4-dimethyl-1,5-pentanonediol, 2-ethyl-4-methyl-1,5-pentenediol, and 2-methyl-4-diol.
  • 2,4-Dialkyl-1,5-pentynediol can be obtained by reacting a 2-butenal derivative with formaldehyde according to a known method, for example, the method described in Japanese Patent Publication No. 8-48642 or EP 807617A. It can be obtained by hydrogenating the obtained reaction product.
  • 2,2-dialkyl-1,3-propanediol examples include 2,2-dipentyl-1,3-propanediol and 2,2-dihexyl-1,3-propanediol.
  • the 2,2-dialkyl-1,3-propanediol can be produced according to a known method, for example, the method described in USP 2,413,803 or JP-A-4-69351.
  • the mixing ratio of 2,4-dialkyl-1,5-pentanediol and 2,2-dialkyl-1,3-propanediol, which are the raw materials of the polyester polyol of the present invention, is 2,4-dialkyl-1,5- It is preferred that the ratio of pendiol to 2,2-dialkyl-1,3-propanediol is 98: 2 to 85:15 (weight ratio).
  • 2,4-Dialkyl-1,5-pentanediol accounts for 85-98% by weight of the total amount of 2,4-dialkyl-1,5-pentanedidiol and 2,2-dialkyl-1,3-propanediol.
  • the mixed polyol of 2,4-dialkyl-1,5-pentanediol and 2,2-dialkyl-1,3-propanediol as a raw material of the polyester polyol is mixed with other diols. Can also be used. In this case, the ratio of the total amount of 2,4-dialkyl-1,5-pentanediol and 2,2-dialkyl-1,3-propanediol in the whole dial is 30% by weight or more, preferably 40% by weight or more.
  • diols include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexandalicol, 3-methyl-1,5-pentanedyl, 1,4-bis (/ 3-hydroxyethoxy) benzene.
  • dicarboxylic acid examples include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid, and among them, succinic acid and adipic acid are preferable. And saturated aliphatic dicarboxylic acids having 4 to 10 carbon atoms, such as azelaic acid and sebacic acid.When these dicarboxylic acids are used, polyurethanes having excellent hydrolysis resistance, alkali resistance and mechanical strength are used. Obtainable.
  • the dicarboxylic acids may be used alone or in combination of two or more.
  • the polyester polyol of the present invention As a raw material of the polyester polyol of the present invention, another dicarboxylic acid other than the dicarboxylic acid may be used in combination.
  • the ratio of the dicarboxylic acid to all dicarboxylic acids is 30% by weight or more, preferably 40% by weight or more.
  • dicarboxylic acids that may be used in combination include, for example, alicyclic dicarboxylic acids such as cyclopropanedicarboxylic acid, and aromatic dicarboxylic acids such as fluoric acid, isofuric acid, and terephthalic acid. can give.
  • the molar ratio of diol to dicarboxylic acid, which is a raw material of the polyester polyol of the present invention is not particularly limited, but is preferably from 1.0 to 2.0.
  • the number average molecular weight of the polyester polyol of the present invention is preferably from 400 to 8,000, more preferably from 700 to 50,000. Polyurethanes using a polyester polyol having a number average molecular weight of more than 8,000 have poor mechanical properties.
  • the polyester resin of the present invention is produced using a conventionally known polyaddition technology. be able to. That is, the polyester polyol obtained above is used as an intermediate, and if necessary, a low molecular weight compound having two or more active hydrogen atoms (chain extender) or the like is uniformly mixed, and the mixture is mixed for about 6 (TC After preheating the mixture, add the polyisocyanate in an amount such that the molar ratio of the number of active hydrogen atoms to the isocyanate group in the mixture becomes 0.95 to 1: 1.05, and stir the mixture with a rotary mixer for a short time.
  • the polyester polyol and the polyisocyanate are preliminarily reacted with each other, and are supplied to the continuous polymerization apparatus having the following formula: These reactions are usually carried out without a solvent, but may be carried out in the presence of dimethylformamide, dimethylsulfoxide, tetrahydrofuran, The reaction can be performed in a solvent such as toluene, etc. These solvents may be used alone or in combination of two or more.
  • polyisocyanate examples include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate and 2,4-tolylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, and hexamethylene diisocyanate. Examples thereof include aliphatic diisocyanates such as nets. These polyisocyanates may be used alone or in combination of two or more.
  • a low molecular compound such as a diol or diamine having two or more active hydrogen atoms
  • the chain extender include diols having 2 to 10 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene diamine, isophorone diamine and the like.
  • Diamines having 2 to 10 carbon atoms may be used alone or in combination of two or more.
  • Use of a chain extender having two active hydrogen atoms such as diol and diamine makes it easy to produce a thermoplastic polyurethane.
  • the amount of the chain extender used is not particularly limited, but is preferably 0.1 to 20 times (molar ratio), more preferably 0.3 to 10 times (molar ratio) with respect to the polyester polyol. Ratio).
  • a monovalent low molecular alcohol such as methanol or ethanol
  • a monovalent low molecular amine such as methylamine or ethylamine
  • the weight average molecular weight of the polyurethane is preferably from 60,000 to 500,000, more preferably from 80,000 to 200,000.
  • the obtained polyurethane can be immediately subjected to molding after polymerization. If the unreacted polyisocyanate is present in the polyurethane in an amount of 0.2% by weight or more depending on the polymerization conditions, aging is performed at 60 to 80 for 4 to 30 hours as needed, and the reaction is completed. Can be attached.
  • a poor solvent for polyurethane for example, an aliphatic saturated hydrocarbon having 6 to 10 carbon atoms such as hexane, heptane, octane, nonane, decane, or methanol, ethanol, etc. is added and mixed. Then, polyurethane can be coagulated and precipitated, filtered, separated, dried, and then subjected to molding.
  • the polyurethane obtained by the present invention can be formed by various methods.
  • the molding method include extrusion molding, injection molding, calendar molding, and blow molding (Plastic Processing Technology Handbook, Nihon Kogyo Shimbun, pages 125, 213, 283, 323, 323, 1969 And 150 to 210 t, preferably 160 to 200 t.
  • Example 1 Extrusion molding, injection molding, calendar molding, and blow molding (Plastic Processing Technology Handbook, Nihon Kogyo Shimbun, pages 125, 213, 283, 323, 323, 1969 And 150 to 210 t, preferably 160 to 200 t.
  • polyester resin of the present invention will be described in more detail with reference to Test Examples and Examples, but the present invention is not limited to the following Examples.
  • Polyester polyester b was synthesized by dehydration polycondensation in the same manner as in Example 1 using 2,4,1-diethyl-1,5-pentanediol 62.19 kg and adipic acid 37.8 lkg.
  • Table 2 shows the physical properties of the obtained polyester polyol b.
  • polyurethanes 1 and 2 were produced by a solventless continuous polymerization method with the compounding composition shown in Table 3.
  • the polymerization equipment and polymerization conditions are as follows.
  • Pre-mixing high speed mixer, rotation speed 100000 rpm, temperature 50-60
  • Polymerization temperature raw material supply port 120: intermediate part 22 O, Die outlet 195 ° C
  • Polymerization time about 150 seconds
  • Table 4 shows the weight average molecular weights of polyurethanes 1 and 2.
  • the weight average molecular weights of polyurethanes 1 and 2 were measured by gel permeation chromatography (GPC) in terms of standard polystyrene.
  • Table 6 shows the weight average molecular weights of the obtained polyurethanes 3 and 4.
  • the weight average molecule t was measured in the same manner as in Example 2.
  • the hydrolysis resistance, alkali resistance and mechanical strength of the polyurethane resins 1-4 obtained as described above were measured as follows.
  • Cylinder numbers are assigned in order of decreasing distance from the raw material charging port.
  • the above polyurethane sheet was subjected to a tensile test at 23 ° C. in accordance with JIS K-7311. Table 7 shows the measurement results.
  • the polyurethanes 1 and 2 of the present invention showed excellent breaking strength as compared with the polyurethanes 3 and 4 of the comparative examples. Hydrolysis resistance
  • Example 2 Using the polyurethane of Example 2 and Comparative Example 2, a polyurethane sheet was produced in the same manner as in the preparation of the sample for measuring physical properties described above, and the polyurethane sheet was placed in warm water held at 70 for 7 days. After immersion for 4 days, 21 days and 28 days, the water was wiped off, and the breaking strength was measured at 23 according to JISK-731. Table 8 shows the measurement results. Table 8
  • the figures in parentheses indicate the retention rate (%) of the initial breaking strength after immersion in warm water.
  • the polyurethanes 1 and 2 of the present invention have higher rupture strength after immersion in hot water than the polyurethanes 3 and 4 of the comparative examples, and also have excellent hydrolysis resistance in terms of retention of rupture strength. However, it can be seen from Table 8. Alkali resistance
  • test pieces having a thickness of 2 mm were produced using an injection molding machine under the following conditions.
  • Injection pressure 20 (Kg / cm 2 )
  • Table 9 shows that the polyurethanes 1 and 2 of the present invention have excellent alkali resistance. Industrial applicability
  • a polyester polyol having two specific structural units as an ester moiety.
  • a polyurethane excellent in hydrolysis resistance, alkali resistance and mechanical strength can be produced. Therefore, the polyurethane can be used for extrusion molding materials such as hoses, tubes, films, sheets, belts, rolls, etc., packing materials, injection molding materials for machine parts, automobile parts, etc., human leather, paints, adhesives, etc. It is useful as a coating material and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des polyesters de polyols dont la molécule renferme à la fois des unités structurelles de formule générale (I), dans laquelle R1 et R2, identiques ou différents, représentent alkyle inférieur comprenant 1 à 8 atomes de carbone, et des unités structurelles de formule générale (II), dans laquelle R3 et R4, identiques ou différents, représentent alkyle inférieur comprenant 1 à 8 atomes de carbone; ainsi que des polyuréthanes produit à partir desdits polyols. Les polyuréthanes ont une excellente résistance à l'hydrolyse et aux bases, une excellente résistance mécanique, etc.
PCT/JP1998/001061 1997-03-27 1998-03-13 Polyurethanes et polyesters de polyols Ceased WO1998044014A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP98907214A EP0908481A4 (fr) 1997-03-27 1998-03-13 Polyurethanes et polyesters de polyols
CA002256627A CA2256627C (fr) 1997-03-27 1998-03-13 Polyurethanes et polyesters de polyols
US09/194,394 US6087466A (en) 1997-03-27 1998-03-13 Polyurethane and polyester polyol
KR1019980709243A KR100306048B1 (ko) 1997-03-27 1998-03-13 폴리우레탄및폴리에스테르폴리올
AU63110/98A AU710285B2 (en) 1997-03-27 1998-03-13 Polyurethanes and polyester polyol
JP54140398A JP3920930B2 (ja) 1997-03-27 1998-03-13 ポリウレタン及びポリエステルポリオール

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7513297 1997-03-27
JP9/75132 1997-03-27

Publications (1)

Publication Number Publication Date
WO1998044014A1 true WO1998044014A1 (fr) 1998-10-08

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PCT/JP1998/001061 Ceased WO1998044014A1 (fr) 1997-03-27 1998-03-13 Polyurethanes et polyesters de polyols

Country Status (9)

Country Link
US (1) US6087466A (fr)
EP (1) EP0908481A4 (fr)
JP (1) JP3920930B2 (fr)
KR (1) KR100306048B1 (fr)
CN (1) CN1113073C (fr)
AU (1) AU710285B2 (fr)
CA (1) CA2256627C (fr)
TW (1) TW446722B (fr)
WO (1) WO1998044014A1 (fr)

Cited By (2)

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WO2001057108A1 (fr) * 2000-02-04 2001-08-09 Kyowa Yuka Co., Ltd. Polyurethanne et resine polyurethanne hydrocompatible
JP4902813B1 (ja) * 2010-12-24 2012-03-21 昭和電工株式会社 高分子量化された脂肪族ポリエステルの製造方法

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CN1154709C (zh) * 1997-07-29 2004-06-23 协和油化株式会社 聚氨酯类粘合剂和其在粘合中使用的方法以及混合物的使用
US6312378B1 (en) * 1999-06-03 2001-11-06 Cardiac Intelligence Corporation System and method for automated collection and analysis of patient information retrieved from an implantable medical device for remote patient care
EP2275468A1 (fr) 2000-07-14 2011-01-19 Metabolix, Inc. Polyurethannes obtenus a partir d'hydroxyalcanoates et d'isocyanates
US20020077269A1 (en) * 2000-10-27 2002-06-20 Whitehouse Robert S. Alkanoic acid ester monomer compositions and methods of making same
JP2004512419A (ja) * 2000-10-27 2004-04-22 メタボリックス・インコーポレーテッド 低分子量ポリヒドロキシアルカノエート含有組成物およびその使用方法
KR100351742B1 (en) * 2001-10-10 2002-09-05 Hosung Chemax Co Ltd Molded article comprising thermoplastic polyurethane consisting of ether-containing polyester polyol
DE10223055A1 (de) * 2002-05-24 2003-12-11 Basf Ag Verfahren zur Herstellung von Polyesterpolyolen mehrwertiger Alkohole
WO2004037890A1 (fr) * 2002-10-28 2004-05-06 Kawasaki Kasei Chemicals Ltd. Polyol de polyester, polyurethane obtenu a partir dudit polyol de polyester, et mousse rigide de polyurethane
CN100487015C (zh) * 2006-10-09 2009-05-13 北京科聚化工新材料有限公司 一种聚氨酯预聚体和其制备方法及其用途
EP2267051A1 (fr) * 2009-05-27 2010-12-29 Sika Technology AG Polyester à silane fonctionnel dans des compositions durcissant à l'humidité à base de polymères à silane fonctionnel
CN103965427B (zh) * 2013-01-25 2018-06-19 科思创聚合物（中国）有限公司 具有长期耐水解性的聚酯型聚氨酯材料

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JP4902813B1 (ja) * 2010-12-24 2012-03-21 昭和電工株式会社 高分子量化された脂肪族ポリエステルの製造方法
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EP0908481A1 (fr) 1999-04-14
EP0908481A4 (fr) 2000-05-31
KR100306048B1 (ko) 2001-11-14
TW446722B (en) 2001-07-21
CN1113073C (zh) 2003-07-02
CA2256627A1 (fr) 1998-10-08
CN1220675A (zh) 1999-06-23
AU6311098A (en) 1998-10-22
AU710285B2 (en) 1999-09-16
US6087466A (en) 2000-07-11
CA2256627C (fr) 2003-05-27
JP3920930B2 (ja) 2007-05-30

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